CN105593190B - The manufacture method of stack-up dielectric ceramic electronic unit and stack-up dielectric ceramic electronic unit - Google Patents

The manufacture method of stack-up dielectric ceramic electronic unit and stack-up dielectric ceramic electronic unit Download PDF

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CN105593190B
CN105593190B CN201480053485.9A CN201480053485A CN105593190B CN 105593190 B CN105593190 B CN 105593190B CN 201480053485 A CN201480053485 A CN 201480053485A CN 105593190 B CN105593190 B CN 105593190B
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stack
dielectric ceramic
molar
electronic unit
ceramic electronic
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CN105593190A (en
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石井秀树
川田慎郎
川田慎一郎
林裕之
奥泽匡
铃木祥郎
铃木祥一郎
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Murata Manufacturing Co Ltd
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Abstract

Stacking sintered body 1 is by using Ni as the internal electrode 3 and piezoceramics layer of principal component, alternately laminated and sintering forms.Piezoceramics layer contains the perovskite-type compounds comprising Nb, K, Na and Li as principal component, and comprising selected from least one of Nd and Dy element M 1 and selected from least one of Ga and Al element M 2.Dissolution process is being carried out in the case of dissolving it, the content of above-mentioned element M 2 is relative to above-mentioned 1 molar parts of Nb for below 0.071 molar part.The stack-up dielectric ceramic piezoelectric part be suppress Ni oxidation reducing atmosphere in by as the conducting film of internal electrode 3 with as piezoceramics layer ceramic green sheet cofiring into and make, be achieved in the good stack-up dielectric ceramic electronic unit of reliability and its manufacture method.

Description

The manufacture of stack-up dielectric ceramic electronic unit and stack-up dielectric ceramic electronic unit Method
Technical field
The present invention relates to the manufacture method of stack-up dielectric ceramic electronic unit and stack-up dielectric ceramic electronic unit, more Specifically, it is related to using Ni as the stacking such as stacked piezo-electric actuator (ア Network チ ュ エ ー タ) of the internal electrode of principal component Type piezoelectric-ceramic electronic part and its manufacture method.
Background technology
In recent years, the stack-up dielectric ceramics such as the stacked piezo-electric actuator of big displacement quantity can be also obtained under small voltage The demand of electronic unit is continuously increased.
Such a stack-up dielectric ceramic electronic unit is usually by that by piezoceramics layer and should become internal electrode and leading Electric layer is alternately laminated and cofiring is into manufacturing.
As internal electrode material, Ag-Pd alloys are widely used all the time, but Ag-Pd alloy ratio basic materials Price higher.Moreover, at this time, if making its driving with low frequency region, D/C voltage, the migration of Ag is easily produced, it is expected using low Migration material.
In order to effectively suppress the generation of such a migration with low cost, preferably using can be bought with lower price using Ni as The internal electrode material of principal component.
On the other hand, if Ni is burnt till in air atmosphere, it is oxidized easily, it is therefore desirable in reducing atmosphere In burnt till, it is therefore desirable to be able to cofiring in reducing atmosphere into piezoelectric.
For this reason, proposing a kind of piezoelectricity chinaware composition in patent document 1, its principal component is with general formula { (1-x) (K1-a- bNaaLib)(Nb1-cTac)O3-xM2M4O3(wherein, at least any a kind in M2 Ca, Ba and Sr, in M4 Zr, Sn and Hf At least any a kind, x, a, b, c are respectively 0.005≤x≤0.1,0≤a≤0.9,0≤b≤0.1,0≤a+b≤0.9,0≤c ≤0.3.) represent, to contain Mn relative to above-mentioned 100 moles of principal component for 2~15 moles of scope, and with relative to upper State 100 moles of principal component and contain above-mentioned M4 for 0.1~5.0 mole of scope.
In the patent document 1, piezoelectricity chinaware composition has above-mentioned composition, so as to improve in reducing atmosphere Agglutinating property, thus, cofiring is carried out into will not recruit under reducing atmosphere with the internal electrode material using Ni as principal component Cause sintering bad, obtain the piezoelectric-ceramic electronic part with good piezoelectric property.
Prior art literature
Patent document
Patent document 1：International Publication No. 2008/152851 (claim 1, (0024))
The content of the invention
Technical problems to be solved by the inivention
It will be appreciated, however, that：Even the piezoelectric-ceramic electronic part of patent document 1, if such as a long time use as actuating In the purposes for needing to apply High Level DC Voltage of device purposes etc, then resistivity reduces, and there is the risk of infringement reliability.Cause This, the piezoelectric-ceramic electronic part of patent document 1 is not suitable for the purposes of reliability more than requirement certain level.
The present invention completes in view of this situation, its purpose is to provide the piezoelectric property for being able to ensure that tolerable practicality and Obtain the stack-up dielectric ceramic electronic unit of good reliability and the manufacturer of stack-up dielectric ceramic electronic unit Method.
For solving the means of technical problem
The inventors of the present invention have made intensive studies in order to achieve the above objectives, as a result obtain following opinion：By making tool The niobic acid alkali metal compound for having perovskite structure contains being selected from selected from least one of Nd and Dy element and ormal weight At least one of Ga and Al element, thus under reducing atmosphere, with using Ni as principal component internal electrode material into Row cofiring is into also ensuring that the piezoelectric property of tolerable practicality and obtain good reliability.
The present invention is in view of such a opinion is completed, stack-up dielectric ceramic electronic unit of the invention, it is characterised in that Be have by it is alternately laminated as the internal electrode and piezoceramics layer of principal component using Ni and in reducing atmosphere sintering form The stack-up dielectric ceramic electronic unit of sintered body is laminated, above-mentioned piezoceramics layer contains the perovskite comprising Nb, K, Na and Li Type compound includes at least one selected from least one of Nd and Dy element M 1 and in Ga and Al as principal component Kind element M 2, in the case where progress dissolution process dissolves it, the content of above-mentioned element M 2 is relative to above-mentioned 1 mole of Nb Part is below 0.071 molar part.
In addition, the stack-up dielectric ceramic electronic unit of the present invention, it is characterised in that had using Ni as principal component Internal electrode and piezoceramics layer it is alternately laminated and in reducing atmosphere sintering form stacking sintered body laminated piezoelectric Ceramic electronic components, above-mentioned piezoceramics layer contain the perovskite-type compounds comprising Nb, K, Na and Li as principal component, and Comprising containing selected from least one of Nd and Dy element M 1 and selected from least one of Ga and Al element M 2, above-mentioned element M 2 Amount is relative to above-mentioned 1 molar parts of Nb for below 0.071 molar part.
In addition, the stack-up dielectric ceramic electronic unit of the present invention, it is characterised in that had using Ni as principal component Internal electrode and piezoceramics layer it is alternately laminated and in reducing atmosphere sintering form stacking sintered body laminated piezoelectric Ceramic electronic components, above-mentioned stacking sintered body contain the perovskite-type compounds comprising Nb, K, Na and Li as principal component, and Comprising containing selected from least one of Nd and Dy element M 1 and selected from least one of Ga and Al element M 2, above-mentioned element M 2 Amount is relative to above-mentioned 1 molar parts of Nb for below 0.071 molar part.
In addition, the stack-up dielectric ceramic electronic unit of the present invention, it is characterised in that had using Ni as principal component Internal electrode and piezoceramics layer is alternately laminated and the stacking sintered body that sinters in reducing atmosphere and in the stacking Stack-up dielectric ceramic electronic unit of the surface of sintered body formed with outer electrode, contains the calcium titanium comprising Nb, K, Na and Li Ore deposit type compound as principal component, and comprising selected from least one of Nd and Dy element M 1 and in Ga and Al at least A kind of element M 2, the content of above-mentioned element M 2 is relative to above-mentioned 1 molar parts of Nb for below 0.071 molar part.
In addition, the stack-up dielectric ceramic electronic unit of the present invention preferably makes the content of above-mentioned element M 2 relative to above-mentioned Nb 1 molar part is more than 0.002 molar part.
In addition, the stack-up dielectric ceramic electronic unit of the present invention preferably makes the content of above-mentioned element M 1 relative to above-mentioned Nb 1 molar part is more than 0.002 molar part and below 0.071 molar part.
In addition, the present invention preferably Mn, Ba, Zr containing ormal weight as needed, it is possible thereby to not damage piezoelectric property In the case of more stably obtain high reliability.
That is, stack-up dielectric ceramic electronic unit of the invention preferably makes above-mentioned piezoceramics layer contain Mn and above-mentioned The content of Mn is relative to above-mentioned 1 molar parts of Nb for below 0.154 molar part.
In addition, the present invention stack-up dielectric ceramic electronic unit preferably make above-mentioned piezoceramics layer contain Ba and on The content of Ba is stated relative to above-mentioned 1 molar parts of Nb as below 0.063 molar part.
In addition, the present invention stack-up dielectric ceramic electronic unit preferably make above-mentioned piezoceramics layer contain Zr and on The content of Zr is stated relative to above-mentioned 1 molar parts of Nb as below 0.088 molar part.
In addition, the manufacture method of the stack-up dielectric ceramic electronic unit of the present invention, it is characterised in that including：Weigh work Sequence, prepare comprising Na compounds, K compounds, Li compounds, Nb compounds, in Nd compounds and Dy compounds at least A kind of compound and plain raw material (the セ ラ ミ ッ Network of ceramics selected from least one of Ga compounds and Al compounds compound Plain raw material), and the above-mentioned plain raw material of each ceramics is weighed so that at least one of Ga and Al element rub after burning till relative to Nb 1 You reach below 0.071 molar part part；Raw cook production process, ceramic green is made using the plain raw material of above-mentioned ceramics as starting material Piece；Conducting film formation process, is coated on above-mentioned ceramic green sheet by the conductive paste using Ni as principal component, forms predetermined pattern Conducting film；Forming process, according to the rules ceramic green sheet of the order stacking formed with conducting film, making are laminated into body；With burn till Process, burns till the above-mentioned body that is laminated into, and makes stacking sintered body；In above-mentioned firing process, suppressing above-mentioned conducting film Oxidation reducing atmosphere in carry out the cofiring of above-mentioned ceramic green sheet and the conductive paste into.
Invention effect
Stack-up dielectric ceramic electronic unit according to the present invention, piezoceramics layer contain the calcium comprising Nb, K, Na and Li Titanium ore type compound as principal component, and comprising selected from least one of Nd and Dy element M 1 and in Ga and Al extremely A kind of few element M 2, in the case where carrying out dissolution process and dissolving it, the content of above-mentioned element M 2 is rubbed relative to above-mentioned Nb 1 Your part is able to ensure that tolerable practicality for below 0.071 molar part by element M 1 and element M 2 both additive effects Property piezoelectric property and realize needed for good reliability.
In addition, it is being alternately laminated with the stacking sintered body of piezoceramics layer, internal electrode and piezoceramics layer and conduct In the stack-up dielectric ceramic electronic unit of finished goods, the content of element M 2 also is defined using 1 molar parts of Nb as benchmark, Therefore element M 2 can play effect similar to the above relative to the content no change of 1 molar parts of Nb.
In addition, the manufacture method of stack-up dielectric ceramic electronic unit according to the present invention, weighs the plain raw material of each ceramics, it Afterwards, by raw cook production process, conducting film formation process and forming process, in the reducing atmosphere of oxidation of conducting film is suppressed The above-mentioned body that is laminated into is burnt till, so that at least one of Ga and Al element reach after burning till relative to 1 mole of Nb Part is total to for the internal electrode material below 0.071 molar part, therefore under reducing atmosphere and using Ni as principal component Burn till, can also obtain the stack-up dielectric ceramic electronic unit with good reliability.
Brief description of the drawings
Fig. 1 is the sectional view for an embodiment for representing the stack-up dielectric ceramic electronic unit of the present invention.
Fig. 2 is laminated into dividing for body for what is obtained in the manufacturing process of the stack-up dielectric ceramic electronic unit of the present invention Solve stereogram.
Fig. 3 is the stereogram of the stack-up dielectric ceramic electronic unit of the present invention.
Fig. 4 is the sectional view of the piezoelectric-ceramic electronic part for an example for representing reference example.
Fig. 5 is the A portions amplification view of Fig. 4.
Fig. 6 is the decomposition for being laminated into body obtained in the manufacturing process of the piezoelectric-ceramic electronic part of above-mentioned reference example Stereogram.
Fig. 7 is the sectional view for the piezoelectric-ceramic electronic part for representing other reference examples.
Embodiment
Fig. 1 is the sectional view for an embodiment for representing the stack-up dielectric ceramic electronic unit of the present invention.
The stack-up dielectric ceramic electronic unit possesses stacking sintered body 1 and is formed at the both ends of the stacking sintered body 1 The outer electrode 2 (2a, 2b) formed by conductive materials such as Ag.Stacking sintered body 1 be by piezoceramics layer and by using Ni as The internal electrode 3 (3a~3g) that the conductive material of principal component is formed is alternately laminated and sinters what is formed.
For being laminated sintered body 1, one end of internal electrode 3a, 3c, 3e, 3g are electrically connected with an outer electrode 2a, interior One end of portion electrode 3b, 3d, 3f are electrically connected with another outer electrode 2b.Moreover, in the stack-up dielectric ceramic electronic unit In, if applying voltage between outer electrode 2a and outer electrode 2b, because of piezoelectric longitudinal effect to the layer shown in arrow X Folded direction displacement.
Moreover, in the present embodiment, form stacking sintered body 1 above-mentioned piezoceramics layer contain comprising Nb, K, Na and The perovskite-type compounds of Li are as principal component, and comprising selected from least one of Nd and Dy element M 1 and selected from Ga and Al At least one of element M 2, carry out dissolution process and make its dissolve in the case of, the content of above-mentioned element M 2 is relative to upper 1 molar parts of Nb are stated as below 0.071 molar part.
Specifically, forming the piezoelectricity chinaware composition of piezoceramics layer can be represented with general formula (A).
100 (K, Na, Li) NbO3+xM1O3/2+yM2O3/2...(A)
That is, for piezoceramics layer using niobic acid alkali based compound as principal component, the niobic acid alkali based compound has A sites by alkali The perovskite type crystal structure that metallic element (K, Na, Li) is formed, B sites are formed by Nb.
Moreover, element M 1 represents at least one kind of element in Nd and Dy, element M 2 is represented in Ga and Al at least 1 kind of element.In addition, x represents M1O3/2Relative to the molar part of 100 molar parts of Nb as principal component, y represents M2O3/2Relatively The molar part of 100 molar parts of Nb in principal component.
Here, in general formula (A), the content of element M 2 is stated relative to 100 molar parts of Nb, using 1 molar parts of Nb as In the case of benchmark, the content of element M 2 is below 0.071 molar part.
, can be to the laminated piezoelectric pottery as finished goods on the composition of the piezoelectricity chinaware composition shown in general formula (A) After porcelain electronic unit removes outer electrode 2a, 2b, carrying out dissolution process with acid etc. makes its dissolving, and ICP-AES (inductance couplings are used to it Close luminescence of plasma spectroscopy apparatus) etc. measurement device carry out quantitative analysis.
Hereinafter, to forming piezoceramics layer in the manner described above the reasons why, is described in detail.
Using niobic acid alkali based compound as in the conventional piezoelectric-ceramic electronic part of principal component, if to outer electrode 2a, 2b Apply DC voltage, then oxygen in lattice is mobile and produce defect.And think that this can impact the behavior of reliability, recruit Reliability is caused to reduce.
For this reason, the inventors of the present invention are to (K, Na, Li) NbO as principal component3Addition element M1 and element M 2 and repeatedly into Row is tested and furtherd investigate, it turns out that：In addition to element M 1, also make element M 2 using relative to 1 molar parts of Nb as 0.071 Scope below molar part contains in piezoceramics layer, and this makes it possible to obtain good reliability.
Speculate that it is to be based on the reasons why following so to obtain good reliability.
One of the reason for being reduced as reliability when applying DC voltage for a long time to outer electrode 2a, 2b, consider such as Under.I.e., as described above, defect is produced because applying DC voltage so as to which the Lacking oxygen in lattice is mobile, piezoceramics layer portion Divide low resistance.It is taken as that：Electric field larger in the segment set beyond the part of low resistance is occurring, as a result piezoelectric ceramics Layer can not bear the big electric field and be destroyed.
If however, addition can be because of ion as the element M 1 of trivalent element, i.e. Nd and/or Dy, element M 1 in principal component The relation of radius and be preferentially solid-solution in A sites as alkali metal site compared to the B sites as Nb sites.Moreover, at this time, by In the alkali metal in A sites with the difference of the ionic radius of element M 1 so as to which lattice is easily deformed, its result can prevent oxygen Atom wants mobile situation.It is thus regarded that can suppress the part low resistance of ceramic layer, can improve it is alive to applying Reliability.
However, even if addition element M1, still since the valence mumber difference between 1 and 1 valency alkali metal of trivalent element M is larger, because This is difficult to the solid solution to A sites, and there is the risk for causing agglutinating property reduction.
Therefore, the element M 2 for belonging to trivalent element and the ormal weight that B sites can be solid-solution in, compensation are added together with element M 1 Element M 1 and the valence mumber of alkali metal are poor.
That is, element M 2 is that Ga and/or Al has and can be solid-solution in the ionic radius in B sites, and valence mumber is trivalent, therefore and A Site, which is compared, can more preferably be solid-solution in B sites.Moreover, thereby compensating for element M 1 and the valence mumber of alkali metal is poor, as a result can Promote solid solution of the element M 1 to A sites, the reduction of agglutinating property will not be caused, improve reliability.
But if the content of element M 2 relative to 1 molar parts of Nb more than 0.071 molar part, agglutinating property can be caused on the contrary Reduction, it is not preferable.Therefore, it is below 0.071 molar part that the content of element M 2, which is needed relative to 1 molar parts of Nb, is preferably More than 0.002 molar part and below 0.071 molar part.
The content of element M 1 is not particularly limited, and is 0.002~0.071 molar part preferably with respect to 1 molar parts of Nb.
It should be noted that speculate that element M 1 and element M 2 produce above-mentioned work by being solid-solution in principal component as described above With effect, as long as but a part for element M 1 and element M 2 is solid-solution in principal component, can also make one part crystal boundary, Crystallize three phase point segregation.
If in addition, also with relative to 1 molar parts of Nb using niobic acid alkali based compound as principal component and in addition to element M 1 Contain element M 2 for the scope below 0.071 molar part, then further preferably as needed containing adding ingredients such as Mn, Ba, Zr.
That is, by making to contain Mn, Ba and/or Zr in principal component, so as to improve agglutinating property in reducing atmosphere, And it can aid in raising reliability.
At this time, forming the piezoelectricity chinaware composition of piezoceramics layer can be represented with general formula (B).
100 (K, Na, Li) NbO3+xM1O3/2+yM2O3/2+zMnO+uBaO+vZrO2...(B)
Z represents contents of the Mn relative to 100 molar parts of Nb as principal component, and u represents that Ba rubs relative to above-mentioned Nb 100 The content of your part, v represent contents of the Zr relative to 100 molar parts of Nb.
But in the case of containing Mn, Ba and/or Zr, if excessively containing these elements, cause piezoelectricity spy The reduction of property, it is not preferable.
That is, if relative to 1 molar parts of Nb, more than 0.154 molar part, excess, presence cause piezoelectric property to the content of Mn The risk of reduction.
In addition, relative to 1 molar parts of Nb, more than 0.063 molar part, if excess, presence cause piezoelectricity spy to the content of Ba Property reduce risk.
Equally, if relative to 1 molar parts of Nb, more than 0.088 molar part, excess, presence cause piezoelectricity spy to the content of Zr Property reduce risk.
Therefore, even if piezoceramics layer does not contain the adding ingredient of Mn, Ba, Zr etc., reliability can also be improved, still, By containing Mn, Ba, Zr, so as to further improve reliability.However, in the case of containing these Mn, Ba, Zr, if Consider piezoelectric property, then it is desirable that relative to 1 molar parts of Nb, Mn for below 0.154 molar part, Ba for 0.063 molar part with Under, Zr is below 0.088 molar part.
Then, the manufacture method of above-mentioned stack-up dielectric ceramic electronic unit is described in detail.
First, as ceramic plain raw material, the alkali metal compound containing Na, K, Li, the Nb chemical combination containing Nb respectively are prepared Thing, the M1 compounds containing element M 1 and the M2 compounds containing element M 2.In addition, prepare the Mn containing Mn respectively as needed Compound, the Ba compounds containing Ba and the Zr compounds containing Zr.It should be noted that the form of compound can be oxidation Any one in thing, carbonate, hydroxide.
Then, alkali metal compound, Nb compounds, M1 compounds and M2 compounds are weighed and makes the element M after burning till 2 Content reaches relative to 1 molar parts of Nb for below 0.071 molar part, and weighs Mn compounds, the Baization of ormal weight as needed Compound and Zr compounds, then, will put into together with the crushing mediums such as these weighed objects and PSZ (partially stabilized zirconium oxide) ball In ball mill, case of wet attrition is fully carried out under ethanol equal solvent, obtains mixture.
Then, after drying the mixture, calcined and synthesized with such as 850~900 DEG C under air atmosphere, obtained Calcined material.
Then, the calcined material so obtained is crushed, afterwards, adds organic bond, dispersant, made with pure water etc. Wet mixed is carried out in the ball mill for decentralized medium, obtains ceramic slurry.Moreover, afterwards, it is formed using scraper plate method etc. Processing, thus makes ceramic green sheet.
Then, the internal electrode conductive paste using Ni as principal component is used, utilizes silk-screen printing as shown in Figure 2 Conducting film 5 (5a~5g) is formed on above-mentioned ceramic green sheet 4 (4a~4g).
Then, after being laminated these ceramic green sheet 4a~4g formed with conducting film 5a~5g, with do not formed conducting film 5a~ Ceramic green sheet 6a, 6b clamping of 5g, crimps it.Moreover, thus make conducting film 5a~5g and ceramic green sheet 4a~4g It is alternately stacked to be laminated into body.Then, this is laminated into body and cuts into given size, house the case (sheath) to oxidation aluminum In, after such as 250~500 DEG C carry out unsticking mixture process, in the case where suppressing the reducing atmosphere of oxidation of Ni with set point of temperature 1000~1100 DEG C are burnt till, and form internal electrode 3a~3g and the alternately stacked stacking sintered body 1 of piezoceramics layer.
Then, the outer electrode conductive paste formed in the both ends coating of stacking sintered body 1 by Ag etc., is providing 750 DEG C~850 DEG C of temperature carries out baking processing, forms outer electrode 2a, 2b as shown in Figure 3.Moreover, afterwards, into professional etiquette Fixed split pole processing, thus manufactures stack-up dielectric ceramic.It should be noted that as long as outer electrode 2a, 2b adaptation is good , such as can be formed using film forming methods such as sputtering method, vacuum vapour depositions.
In this way, the manufacture method of above-mentioned stack-up dielectric ceramic electronic unit includes：Process is weighed, preparation includes Na chemical combination Thing, K compounds, Li compounds, Nb compounds, selected from least one of Nd compounds and Dy compounds compound, Yi Jixuan From the plain raw material of ceramics of at least one of Ga compounds and Al compounds compound, and weigh the above-mentioned plain raw material of each ceramics so that At least one of Ga and Al element reach below 0.071 molar part after burning till relative to 1 molar parts of Nb；Raw cook makes work Sequence, ceramic green sheet is made using the plain raw material of above-mentioned ceramics as starting material；Conducting film formation process, by leading using Ni as principal component Conductive paste is coated on above-mentioned ceramic green sheet, forms the conducting film of predetermined pattern；Forming process, according to the rules order stacking are formed There is the ceramic green sheet of conducting film, making is laminated into body；And firing process, the above-mentioned body that is laminated into is burnt till, makes layer Laminated sinter；In above-mentioned firing process, above-mentioned ceramic green sheet is carried out in the reducing atmosphere of oxidation of above-mentioned conducting film is suppressed Therefore cofiring with the conductive paste under reducing atmosphere to ceramic green sheet and by principal component of Ni into, leading Electrolemma carries out cofiring into can also obtain ensuring the piezoelectric property of tolerable practicality and the laminated piezoelectric with good reliability Ceramic electronic components.
It should be noted that the present invention is not limited to the above embodiment.For example, in the above-described embodiment, carry out Dissolution process and make its dissolving, extract sample, composition analysis is carried out to it, even in be alternately laminated with piezoceramics layer, The stacking sintered body of internal electrode and piezoceramics layer and as finished goods stack-up dielectric ceramic electronic unit as trying In the case of sample, the content of element M 2 is limited on the basis of 1 molar parts of Nb, therefore element M 2 is relative to the member of 1 molar parts of Nb The content of plain M2 does not change, and can play effect similar to the above.
In addition, as long as principal component belongs to the material of the category of niobic acid alkali based compound, used by a part of Nb In the case that Ta is replaced, action effect similar to the above can be also obtained.
In addition, in the above-described embodiment, element M 1 is set to Nd and/or Dy, as long as but comprising Nd and/or Dy, For example, a part of ionic radius that can be replaced into K, Na of Nd or Dy and the difference of the ionic radius of Nd, Dy are equal or equal Rare earth element above is such as Sc, In, Y, Eu, Gd, Sm, Ho, Er, Tb.
In addition, in the above-described embodiment, element M 2 is set to Ga and/or Al, as long as but comprising Ga and/or Al, The elements such as a part of Cr, Fe that can be replaced as with the ionic radius that can be solid-solution in B sites and for trivalent element of Ga or Al.
Then, the embodiment of the present invention is specifically described.
Embodiment
First, as ceramic plain raw material, K is prepared2CO3、Na2CO3、Li2CO3、Nb2O5、BaCO3、ZrO2、MnCO3、Dy2O3、 Nd2O3、Ga2O3And Al2O3。
Moreover, in general formula (100 (K0.49Na0.49Li0.02)NbO3+xM1O3/2+yM2O3/2+zMnO+uBaO+vZrO2) in, into Row weighs and makes M1, M2, x, y, z, u, v as the composition shown in table 1.
Then, these weighed objects are put into ball mill together with PSZ balls, is fully carried out using ethanol as decentralized medium Wet mixed.Then, after the mixture of gained is dried, when small with 850 DEG C of temperature calcination 2 in air atmosphere, forged Burn thing.
Then, after these calcined materials are crushed, which is put into ball milling together with adhesive, dispersant and pure water In machine, wet mixed is fully carried out, afterwards, implements to form using scraper plate method, obtains the ceramic green sheet of 120 μm of thickness.
Then, prepare the conductive paste using Ni as principal component, using silk screen print method, led to ceramic green sheet coating is above-mentioned Conductive paste, forms the conducting film of predetermined pattern.
Then, order is laminated the ceramic green sheet formed with conducting film according to the rules, pressurizes under the pressure of 25MPa, After crimping, (specimen coding 1~23 and 26~32) or air atmosphere (specimen coding in the case where suppressing the reducing atmosphere of oxidation of Ni 24~25 and 33) under with 1000~1100 DEG C of temperature burn till 2 it is small when, thus make piezoceramics layer and internal electrode alternating layer The folded stacking sintered body formed.
Moreover, alternately revealed from the both ends of the surface of stacking sintered body with the above-mentioned stacking sintered body of dicer cut-out but internal electrode Go out, then, sputter process is carried out to both ends of the surface, forms the external electrical for the two-layer structure being made of Ni-Cr alloy and Ni-Cu alloys Pole, thus obtains the sample of specimen coding 1~33.It should be noted that the appearance and size of each sample is length 8.0mm, width 2.0mm, thickness 1.0mm, stacking number are 11 layers.
(evaluation of sample)
To each sample of specimen coding 1~33, apply the electric field of 10 minutes 3.0kV/mm at room temperature, carry out split pole processing Afterwards, using laser-Doppler (laser Doppler) vibrometer, apply the electric field of 0.5~11kV/mm, measuring frequency 1kHz The displacement S of the width of lower measure element, by displacement S divided by element width (2.0mm), tries to achieve strain, then should Strain divided by electric field E, calculate the S/E values of each electric field, and placement property is evaluated with the maximum Smax/Emax of S/E values.
Then, each sample of specimen coding 1~33 is put into 85 DEG C of thermostat, applies the DC electric fields of 2kV/mm, Respectively after input, by 1 it is small when, 24 it is small when, 100 it is small when, 200 it is small when, 300 it is small when, 400 it is small when and 500 it is small when at the time of Sample is taken out from thermostat, measures resistivity.Moreover, resistivity is reached 103As DC electric fields at the time of below Ω cm The reliable life of application.
In addition, to each sample of specimen coding 1~33, the stacking sintered body acid after removing outer electrode is dissolved, is made Composition analysis is carried out with ICP-AES (inductively coupled plasma emission spectrophotometer).
The component composition and firing atmosphere of 1 representing sample numbering 1~33 of table, table 2 represent each component relative to 1 mole of Nb The molar part, Smax/Emax values and reliable life of part.
[table 1]
* 1) it is in outside claim 1 scope
* 2) it is in outside claim 7 scope
* 3) it is in outside claim 8 scope
* 4) it is in outside claim 9 scope
[table 2]
* 1) it is in outside claim 1 scope
* 2) it is in outside claim 7 scope
* 3) it is in outside claim 8 scope
* 4) it is in outside claim 9 scope
Understand：In specimen coding 1, piezoceramics layer does not include any one of element M 1 and element M 2, therefore Smax/ Emax values for 120pm/V and placement property is good, but reliable life for 24 it is small when, poor reliability.
In specimen coding 2 and 3, although comprising element M 1, do not include element M 2, thus can not make its 1000~ 1100 DEG C of temperature fully sinters, and can not measure placement property and reliable life.
Confirm：In specimen coding 4, although comprising element M 2, element M 1, therefore Smax/Emax values are not included For 7pm/V, placement property is poor, and reliable life be also as short as 24 it is small when, reliability is also poor.
In specimen coding 20, although comprising element M 1 and element M 2, the content of element M 2 is relative to 1 mole of Nb Part excess for 0.073 molar part.Therefore, it is impossible to make it fully be sintered with 1000~1100 DEG C of temperature, and can not measure Placement property and reliable life.
Equally, in specimen coding 31, although comprising element M 1 and element M 2, the content of element M 2 is relative to Nb 1 Molar part excess for 0.074 molar part, therefore, with specimen coding 20 equally it can not fully sinters, and can not measure Placement property and reliable life.
Specimen coding 24~25 and 33 is burnt till in air atmosphere, therefore the Ni hairs of the principal component as internal electrode Raw oxidation, therefore placement property and reliable life can not be measured.
In this regard, understand：Specimen coding 5~19,21~23,26~30 and 32 relative to 1 molar parts of Nb as 0.071 to rub Scope below your part contains element M 2, and also contains element M 1, thus be able to ensure that 300 it is small when more than the reliability longevity Life, and good reliability can be obtained.
But, it is known that：In specimen coding 10, the content of Ba relative to 1 molar parts of Nb for 0.067 molar part excess, Therefore Smax/Emax values become 10pm/V and placement property reduces.That is, can be clear and definite by specimen coding 8：If in addition to element M 1 with Contain element M 2 for the scope below 0.071 molar part relative to 1 molar parts of Nb, even if not containing Ba then, also ensure that Smax/Emax values are more than 30pm/V.It will be appreciated, however, that：If the content of Ba relative to 1 molar parts of Nb more than 0.063 molar part, Although then reliability is good, placement property reduces, therefore in the case of containing Ba, the content of Ba is preferably with respect to Nb 1 Molar part is below 0.063 molar part.
In addition, understand：In specimen coding 13, due to Zr content relative to 1 molar parts of Nb for 0.091 molar part and It is excessive, therefore the placement property reduction for 19pm/V of Smax/Emax values.That is, can be clear and definite by specimen coding 7：If remove element M 1 , also can be true even if not containing Zr then outside also to contain element M 2 as the scope below 0.071 molar part relative to 1 molar parts of Nb It is more than 30pm/V to protect Smax/Emax values.But understand：If the content of Zr relative to 1 molar parts of Nb more than 0.088 molar part, Although then reliability is good, placement property reduces, therefore in the case of containing Zr, when Nb is set to 1 molar part, preferably Below 0.088 molar part.
In addition, understand：In specimen coding 17, the content of Mn relative to 1 molar parts of Nb for 0.169 molar part excess, Therefore Smax/Emax values placement property reduction for 17pm/V.That is, can be clear and definite by specimen coding 14：If in addition to element M 1 also To contain element M 2 as the scope below 0.071 molar part relative to 1 molar parts of Nb, even if not containing Mn then, also ensure that Smax/Emax values are more than 30pm/V.But understand：If the content of Mn relative to 1 molar parts of Nb more than 0.154 molar part, Although reliability is good, placement property reduces, therefore in the case of containing Mn, is preferably when Nb is set to 1 molar part Below 0.154 molar part.
Reference example
Understand：In the above-mentioned present invention, by making to contain element M 1 (Nd and/or Dy) in piezoceramics layer and making Contain relative to 1 molar parts of Nb for the element M 2 (Ga and/or Al) below 0.071 molar part together with principal component and make pottery in piezoelectricity In enamel coating, so that reliability improves, and the result of study of people etc. according to the present invention, make pottery as the piezoelectricity of stacking sintered body Porcelain ferritic is divided into skin section region and skin section exterior domain, Ga, Nd and the Dy in skin section region is contained mole ratio table Layer portion exterior domain is more, so as to can also obtain good reliability.
Hereinafter, which is recited as reference example.
Fig. 4 is the sectional view for the single panel type piezoelectric-ceramic electronic part for being exemplarily shown as reference example.
The piezoelectric-ceramic electronic part forms a pair of external electrodes 102a, 102b in two interareas of piezoelectric ceramics ferritic 101, If applying voltage between these outer electrodes 102a and outer electrode 102b, to arrow Y-direction displacement.
Same with the present invention for piezoelectric ceramics ferritic 101, principal component is by the niobic acid alkali system with perovskite structure Compound is formed, and contains Ga as accessory ingredient, and contains at least element M 3 of any one in Nd and Dy.
Fig. 5 is A portions amplification view, represents outer electrode 102a and area near the joint interface of piezoelectric ceramics ferritic 105 Domain.It should be noted that although diagram is omitted, near the joint interface of outer electrode 102b and piezoelectric ceramics ferritic 101 Region is similarly.
That is, which is divided into the top layer with the thickness t of the outer electrode 102a thickness directions contacted The portion region 101a and skin section exterior domain 101b in addition to above-mentioned skin section region.Moreover, form above-mentioned skin section region 101a and make Ga/Nb than, Nd/Nb when Dy/Nb than total it is more than skin section exterior domain 101b, it is possible thereby to remain good The raising of reliability is realized while piezoelectric property.
Think so to maintain good piezoelectric property and improve reliability be based on it is following the reasons why.
Piezoelectric ceramics ferritic 101 is typically that formed body is burnt till to make, but with niobic acid alkali based compound In the case of forming principal component, contained alkali metal is steamed when burning till from the surface of formed body in niobic acid alkali based compound Hair, as a result thinks that the skin section region 101a of the piezoelectric ceramics ferritic 101 after burning till produces defect, this can become reliability and drop The reason for low.
However, the result of study of people etc. according to the present invention, in the niobic acid alkali based compound as principal component containing Ga and Element M 3 (Nd and/or Dy) evaluates characteristic as accessory ingredient, although as a result reliability improves, causes the drop of piezoelectricity It is low.
For this reason, further being furtherd investigate, following achievement is as a result obtained：Piezoelectric ceramics ferritic 101, which is divided into, to be become Outside the skin section for easily producing the skin section region 101a of surface defect and not producing surface defect for the reason for reliability reduces Region 101b, make the Ga/Nb of skin section region 101a than, Nd/Nb and Dy/Nb than total it is more than skin section exterior domain 101b, Thus in the case that long-time applies DC voltage, still good piezoelectric property is ensured in skin section exterior domain 101b, And skin section region 101a suppress surface defect generation, the reduction of piezoelectricity will not be caused, it is possible to increase reliability.
So in piezoelectric ceramics ferritic 101, principal component is formed by the niobic acid alkali based compound with perovskite structure, And contain Ga as accessory ingredient, at the same time containing at least element of any one in Nd and Dy, and it is divided into skin section region 101a With the skin section exterior domain 101b in addition to the 101a of the skin section region, make the Ga/Nb ratios of skin section region 101a, Nd/Nb when Dy/Nb than total it is more than skin section exterior domain 101b, it is possible thereby to maintain good piezoelectric property and obtain good reliable Property, it is possible thereby to take into account piezoelectric property and reliability.
It should be noted that for improve piezoelectric property the purpose of, further preferably make piezoelectric ceramics ferritic 101 containing it is various into Point.For example, further preferably make ANbO3In contain suitable formula M 2M4O3(M2 represent Ba, Ca and Sr at least any one, M4 Represent at least one kind of in Zr, Sn and Hf.) shown in compound and form the niobic acid alkali based compound as principal component, thus, it is possible to It is enough further to improve piezoelectric property.
The piezoelectric-ceramic electronic part of above-mentioned reference example can be easily manufactured in the following way.
First, as ceramic plain raw material, alkali metal compound, Nb compounds, Ga compounds, the M3 containing element M 3 are prepared Compound, further according to needing to prepare Ba compounds, Zr compounds etc..
Then, after the above-mentioned plain raw material of ceramics of ormal weight is weighed, by these weighed objects put into set PSZ (part be steady Surely zirconium oxide is changed) in the ball mill of crushing medium such as ball, abundant case of wet attrition, obtains mixture under ethanol equal solvent.
Then, after drying the mixture, calcined and synthesized at 850~900 DEG C, obtain calcined material.
Then, the calcined material so obtained is crushed, afterwards, organic bond, dispersant is added, using pure water etc. as molten Agent carries out wet mixed in the ball mill, obtains ceramic slurry.Moreover, afterwards, being formed using implementations such as scraper plate methods, make As shown in Figure 6 the first ceramic green sheet 103 and the thickness t after burning till is reached such as 120 μm.
Then, weigh the plain raw material of ceramics and make Ga/Nb when M3/Nb than ceramic green sheet 103 of the total amount than first it is few, remove Beyond this, using the method and step same with the first ceramic green sheet 103, make second ceramic green sheet 104 shown in Fig. 6 and The thickness t after burning till is set to reach such as 120 μm.
Then, after the second ceramic green sheet 104 of stacking regulation the piece number, by the second ceramic green sheet 104 being laminated with above-mentioned First ceramic green sheet 103 clamps, and is crimped.The first ceramic green sheet 103 is configured at outermost layer moreover, thus making Build up body.
Then, body will be laminated into and cuts into given size, be contained in the case (sheath) of oxidation aluminum, at 250~500 DEG C After carrying out unsticking mixture process, burnt till under reducing atmosphere with 1000~1100 DEG C, form (the stacking of piezoelectric ceramics ferritic Sintered body) 101.
Then, the outer electrode conductive paste that coating is formed by Ag etc. on the surface of piezoelectric ceramics ferritic 101, 750 DEG C~850 DEG C progress calcination process, form outer electrode 102a, 102b.Moreover, afterwards, split pole as defined in progress is handled, Thus piezoelectric-ceramic electronic part is manufactured., can it should be noted that as long as outer electrode 102a, 102b adaptation is good To be formed using the film forming method such as sputtering method, vacuum vapour deposition.
Then, as other reference examples, stack-up dielectric ceramic electronic unit is described.
Fig. 7 is the sectional view for the stack-up dielectric ceramic electronic unit for being exemplarily shown as other reference examples.
(with reference to Fig. 1) substantially same with the present invention, the stack-up dielectric ceramic electronic unit possess stacking 105 He of sintered body It is formed at the outer electrode 106a, the 106b that are formed by conductive materials such as Ag at the both ends of the stacking sintered body 105.Stacking is burnt Knot body 105 is the piezoceramics layer of gained will to be burnt till to ceramic green sheet and formed by the conductive material using Ni as principal component Internal electrode 107 is alternately laminated to be formed.
In other reference examples, for being laminated sintered body 105, principal component is by the niobic acid alkali with perovskite structure Based compound is formed, and contains Ga as accessory ingredient, the element M at the same time containing at least one of Nd and Dy.
In the figure 7, A ' portions are substantially same with Fig. 5 of previous reference example, and stacking sintered body 105 is divided into skin section area Domain and skin section exterior domain, form skin section region and make Ga/Nb than, Nd/Nb when Dy/Nb than total than skin section outskirt Domain is more, thus, same with previous reference example, maintains good piezoelectric property, and realize the raising of reliability.
It should be noted that in other reference examples, as internal electrode material, using low cost and can suppress to migrate Generation the material using Ni as principal component, it is therefore desirable to burnt till in reducing atmosphere, it is therefore desirable for containing Mn or Zr As accessory ingredient and improve the agglutinating property in reducing atmosphere.
The laminated piezoelectric type ceramic electronic components make composition different in skin section region with skin section exterior domain, except this with Outside, can be made (with reference to Fig. 2,3) using the method and step same with the present invention.
It is also same with the present invention so in other reference examples, under reducing atmosphere and using Ni as principal component Internal electrode material carries out cofiring into can also obtain the good stack-up dielectric ceramic electronic unit of reliability.
(experimental example)
To the stack-up dielectric ceramic electronic unit shown in other reference examples, sample is made, evaluates characteristic.Hereinafter, Its experimental example is specifically explained.
(making of sample)
(making of ceramic green sheet)
First, as ceramic plain raw material, K is prepared2CO3、Na2CO3、Nb2O5、BaCO3And ZrO2.Then, above-mentioned ceramics are weighed Plain raw material makes composition formula become (100 { 0.95 (K0.5Na0.5)NbO3-0.05BaZrO3}+0.5ZrO2〕.Then, these are weighed Thing put into set in the ball mill of PSZ balls, carried out using ethanol as solvent about 90 it is small when wet mixed.Then, to gained After mixture is dried, is calcined in air atmosphere with 850 DEG C of temperature, obtain calcined material.
Then, as the plain raw material of other ceramics, MnCO is prepared3、Ga2O3、Nd2O3And Dy2O3, relative to these calcined materials 1 Molar part, adds the MnCO of 0.05 molar part3, in addition, addition Ga2O3、Nd2O3And Dy2O3Make Ga, Nd and Dy containing mole Amount reaches molar part shown in table 3 relative to 1 molar part of calcined material, is crushed, obtains mixture.
Then, which is put into ball mill together with adhesive, dispersant and pure water, abundant wet mixed, it Afterwards, implement to form using scraper plate method, make the ceramic green sheet of specimen coding A~F of 120 μm of the thickness of regulation the piece number.
Ga, Nd and Dy containing relative to 1 molar part of calcined material in each ceramic green sheet of 3 representing sample numbering A~F of table Mole.
[table 3]
(making of evaluation sample)
Prepare the conductive paste using Ni as principal component, in above-mentioned ceramic green sheet, silk is used to a part of ceramic green sheet Net print process is coated with above-mentioned conductive paste, forms the conducting film of predetermined pattern.
Then, appropriate laminated ceramic raw cook A~F and make beyond ceramic green sheet and the skim-coat portion region in skin section region The combination of the ceramic green sheet of skin section exterior domain forms as table 4 and is laminated into body.
Skin section region and the group of ceramic green sheet A~F of skin section exterior domain in 4 representing sample numbering 101~107 of table Close.In addition, stacking number is 11 layers.
[table 4]
Then, body pressurization is laminated into this with the pressure of 25MPa, after crimping, in the reproducibility gas for the oxidation for suppressing Ni In atmosphere with about 1000~1080 DEG C of temperature burn till 2 it is small when, thus make and be embedded with the stacking sintered body of internal electrode.
Then, above-mentioned piezoelectric ceramics ferritic is cut off with dicer and hands over the both ends of the surface of internal electrode from stacking sintered body For exposing, then, sputter process is carried out to both ends of the surface, form the outer of the two-layer structure that is made of Ni-Cr alloy and Ni-Cu alloys Portion's electrode, further applies the electric field of the 3.0kV/mm of 10 minutes in room temperature, carries out split pole processing, thus obtain specimen coding 101~107 sample.It should be noted that the appearance and size of each sample is length 8.0mm, width 2.0mm, thickness 1.0mm.
(evaluation of sample)
Mirror ultrafinish is carried out to a part for each sample of specimen coding 101~107, uses FE-WDX (field emission formulas Wavelength-dispersion type X-ray diffraction device), to the composition analysis each 5 of the arbitrary point within 5 μm of skin section and within 5 μm of central portion Point, obtain Ga/Nb than, Nd/Nb than, Dy/Nb than average value.
In addition, to each sample of specimen coding 101~107, it is same with the present invention, using LASER DOPPLER VIBROMETER, apply Add the electric field of 0.5~11kV/mm, the displacement S of the width of element is measured in the case where measuring frequency 1kHz, displacement S is removed With element width (2mm), strain is tried to achieve, then by the strain divided by electric field E, the S/E values of each electric field are calculated, with the maximum of S/E values Value Smax/Emax evaluates placement property.
In addition, each sample of specimen coding 101~107 is put into 85 DEG C of thermostat, apply the DC electricity of 2kV/mm , respectively after input, by 1 when small, 24 it is small when, 100 it is small when, 200 it is small when, 300 it is small when, 400 it is small when and 500 it is small when when Quarter takes out sample from thermostat, measures resistivity.Moreover, resistivity is reached 103The time point of below Ω cm is as DC electricity The reliable life that field applies.
The skin section of 5 representing sample numbering 101~107 of table and the Ga/Nb ratios of central portion, Nd/Nb ratios, Dy/Nb ratios are (average Value), Smax/Emax values and reliable life.
[table 5]
Understand：In specimen coding 107, any one of Ga, Nd and Dy, therefore, Smax/ are not contained in skin section region Emax values for 120pm/V and it is good, reliable life be as short as 24 it is small when, poor reliability.
In addition, understand：In specimen coding 106, although containing Ga and Dy, Ga/Nb when Dy/ in skin section region Nb than total it is identical with skin section exterior domain, do not produced in skin section region and skin section exterior domain substance concentration difference, Therefore reliable life for 500 it is small when and good, Smax/Emax values as low as 60pm/V, placement property are poor.
In this regard, confirm：In specimen coding 101~105, the Ga/Nb ratios in skin section region, Nd/Nb when Dy/Nb ratios Total it is bigger than skin section exterior domain, therefore Smax/Emax values can ensure that good placement property for 80~107pm/V, this Outside, reliable life also for 400~500 it is small when obtain good reliability.
Symbol description
1 stacking sintered body
2a, 2b outer electrode
3a~3g internal electrodes

Claims (9)

  1. A kind of 1. stack-up dielectric ceramic electronic unit, it is characterised in that be with by using Ni as principal component internal electrode and Piezoceramics layer is alternately laminated and sinters the stack-up dielectric ceramic ministry of electronics industry of the stacking sintered body formed in reducing atmosphere Part,
    The piezoceramics layer contains the perovskite-type compounds comprising Nb, K, Na and Li as principal component, and comprising selected from At least one of Nd and Dy element M 1 and selected from least one of Ga and Al element M 2,
    In the case where progress dissolution process dissolves it, the content of the element M 2 is relative to 1 molar parts of Nb More than 0.002 molar part and below 0.071 molar part.
  2. A kind of 2. stack-up dielectric ceramic electronic unit, it is characterised in that be with by using Ni as principal component internal electrode and Piezoceramics layer is alternately laminated and sinters the stack-up dielectric ceramic ministry of electronics industry of the stacking sintered body formed in reducing atmosphere Part,
    The piezoceramics layer contains the perovskite-type compounds comprising Nb, K, Na and Li as principal component, and comprising selected from At least one of Nd and Dy element M 1 and selected from least one of Ga and Al element M 2,
    The content of the element M 2 is relative to 1 molar parts of Nb for more than 0.002 molar part and below 0.071 molar part.
  3. A kind of 3. stack-up dielectric ceramic electronic unit, it is characterised in that be with by using Ni as principal component internal electrode and Piezoceramics layer is alternately laminated and sinters the stack-up dielectric ceramic ministry of electronics industry of the stacking sintered body formed in reducing atmosphere Part,
    It is described stacking sintered body contain the perovskite-type compounds comprising Nb, K, Na and Li as principal component, and comprising selected from At least one of Nd and Dy element M 1 and selected from least one of Ga and Al element M 2,
    The content of the element M 2 is relative to 1 molar parts of Nb for more than 0.002 molar part and below 0.071 molar part.
  4. A kind of 4. stack-up dielectric ceramic electronic unit, it is characterised in that be with by using Ni as principal component internal electrode and Piezoceramics layer is alternately laminated and stacking sintered body and in the table of the stacking sintered body that sintering forms in reducing atmosphere Stack-up dielectric ceramic electronic unit of the face formed with outer electrode,
    Contain the perovskite-type compounds comprising Nb, K, Na and Li as principal component, and comprising in Nd and Dy at least A kind of element M 1 and selected from least one of Ga and Al element M 2,
    The content of the element M 2 is relative to 1 molar parts of Nb for more than 0.002 molar part and below 0.071 molar part.
  5. 5. stack-up dielectric ceramic electronic unit according to any one of claims 1 to 4, it is characterised in that the member The content of plain M1 is relative to 1 molar parts of Nb for more than 0.002 molar part and below 0.071 molar part.
  6. 6. stack-up dielectric ceramic electronic unit according to any one of claims 1 to 4, it is characterised in that the pressure Electroceramics layer contains Mn, and
    The content of the Mn is relative to 1 molar parts of Nb for below 0.154 molar part.
  7. 7. stack-up dielectric ceramic electronic unit according to any one of claims 1 to 4, it is characterised in that the pressure Electroceramics layer contains Ba, and
    The content of the Ba is relative to 1 molar parts of Nb for below 0.063 molar part.
  8. 8. stack-up dielectric ceramic electronic unit according to any one of claims 1 to 4, it is characterised in that the pressure Electroceramics layer contains Zr, and
    The content of the Zr is relative to 1 molar parts of Nb for below 0.088 molar part.
  9. A kind of 9. manufacture method of stack-up dielectric ceramic electronic unit, it is characterised in that including：
    Weigh process, prepare comprising Na compounds, K compounds, Li compounds, Nb compounds, selected from Nd compounds and Dy chemical combination At least one of thing compound and the ceramics element original selected from least one of Ga compounds and Al compounds compound Material, and the plain raw material of each ceramics is weighed so that at least one of Ga and Al element reach after burning till relative to 1 molar parts of Nb More than to 0.002 molar part and below 0.071 molar part；
    Raw cook production process, ceramic green sheet is made using the plain raw material of the ceramics as starting material；
    Conducting film formation process, is coated on the ceramic green sheet by the conductive paste using Ni as principal component, forms predetermined pattern Conducting film；
    Forming process, according to the rules ceramic green sheet of the order stacking formed with conducting film, making are laminated into body；With
    Firing process, burns till the body that is laminated into, and makes stacking sintered body,
    In the firing process, carried out in the reducing atmosphere of oxidation of the conducting film is suppressed the ceramic green sheet with it is described The cofiring of conductive paste into.
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